Diallyl carbonate filled compositions

ABSTRACT

Compositions comprising diallyl carbonate polymers and at least a primary filler such as alpha cellulose, glass fibers, polyester fibers, and mixtures thereof have better stain resistance and better impact resistance and other strength properties than prior art compositions recognized as outstanding for use in dinnerware. The compositions can also contain such secondary fillers as clay, calcium carbonate, magnesium carbonate, silica powder and the like. They also have excellent hardness and resistance to chemical attack by alkali and detergents and have excellent hightemperature properties.

United States Patent Berry et a1.

[ Feb. 22, 1972 [54] DIALLYL CARBONATE FILLED COMPOSITIONS [72]Inventors: David A. Berry, Columbus; Gilbert M. Gynn, Hilliard, both ofOhio [73] Assignee: Dart Industries Inc.

[22] Filed: Apr. 16, 1969 [21} Appl. No.: 816,794

[52] [1.8. CI ..260/ 17.4 CL, 260/22 CB, 260/23.5 R,

260/32.8 R, 260/40 P, 260/41 A, 260/41 AG, 260/41 B, 260/41 C Loritsch..260/78.5

Primary Examiner-William M. Short Assistant ExaminerLouise P. QuastAttorney-Ronald J. Carlson, Fred S. Valles and Richard A.

, Dannels, Jr.

[57] ABSTRACT Compositions comprising diallyl carbonate polymers and atleast a primary filler such as alpha cellulose, glass fibers, polyesterfibers, and mixtures thereof have better stain resistance and betterimpact resistance and other strength properties than prior artcompositions recognized as outstanding for use in dinnerware. Thecompositions can also contain such secondary fillers as clay, calciumcarbonate, magnesium carbonate, silica powder and the like. They alsohave excellent hardness and resistance to chemical attack by alkali anddetergents and have excellent high-temperature properties.

6 Claims, No Drawings DIALLYL CARBONATE FILLED COMPOSITIONS BACKGROUNDOF THE INVENTION l. Field of the Invention This invention relates tocompositions of matter containing a reinforcing filler. Moreparticularly, it relates to the reinforcement of diallyl carbonatepolymers by blending with a certain type of fibrous material such ascellulose, glass and polyester fibers to thereby improve certainspecific physical properties making the diallyl carbonate polymers idealfor use in dinnerware and laminated tabletops.

Compositions of this invention find use in injection andcompression-molded articles of thermosetting resins. The resultingarticles have high heat resistance, high modulus of elasticity, hightensile strength, high impact strength, and excellent hardness, solventresistance, and resistance to staining and particularly staining causedby coffee, tea, fruit and vegetable juices of all types, soft drinks andthe like. Another important physical property possessed by the articlesmolded from the compositions of this invention is their very low wickeffect, that is, their low ability to pick up color bodies through theporous edges left on the articles during the molding operation andscratches produced during their use. A pronounced wick effect isexperienced with articles from the prior art compositions which effectcauses marked discoloration adjacent to the porous edges of thearticles. Because of these excellent physical properties, the heatandpressure-consolidated resinous articles have ideal applications indinnerware, i.e., flatware including cups, saucers, plates and the likeand in laminated table, bar and counter tops.

2. Description of the Prior Art Copolymers of diallyl carbonate with,for example, diallyl phthalate are known in the prior art; see U.S. Pat.No. 2,514,354. Such copolymers have been found to be acid and alkaliresistant and have lower brittleness than diallyl carbonatehomopolymers, permitting their use as interior coatings for storingfruits, juices, and the like. However, such copolymers do not have thecombination of properties of the compositions of the present invention.In addition, these copolymers have been found to be very costly due tothe necessity for employing both types of expensive monomers, i.e.,diallyl carbonate and diallyl phthalate, to achieve the desired physicalproperties.

Certain fillers, such as powdered alpha cellulose, have been added tomolding compositions consisting of, e.g., ethylene glycol bis (alkylcarbonate), to yield translucent products which though strong have notbeen found suitable to withstand the severe conditions required fordinnerware; see U.S. Pat. No. 2,403,112. In addition, such prior artcompositions were not found to have the excellent resistance to stainingpossessed by the present compositions.

Melamine-formaldehyde resins have experienced widespread use in moldedarticles such as dinnerware. However, one of the major disadvantages ofsuch resins is their susceptibility to the various kinds of stains fromcoffee and the like as discussed above. Attempts to modify themelaminetype resins to make them resistant to staining have alsorequired rather costly components; see U.S. Pat. No. 3,367,917.

SUMMARY The compositions of the present invention which when convertedto molded articles have very high flexural strength, tensile strengthand hardness and have greatly improved stain resistance and impactresistance when compared to the prior art compositions.

An object of the present invention is to provide filled compositions ofdiallyl carbonate that have improved physical properties over the priorart compositions. Another object of this invention is to providerelatively low-cost filled diallyl carbonate compositions which haveoutstanding physical properties suitable for use in dinnerware.

The present invention provides a composition of matter comprising anintimate blend of at least 35 weight percent of a polymer containing atleast 50 weight percent of diallyl carbonate, and at least 25 percent ofone or more reinforcing fillers. The reinforcing fillers comprise atleast 10 weight percent of a primary filler and O to 40 weight percentof a secondary filler. The primary filler is selected from the groupconsisting of cellulose, glass and polyester fibers and mixturesthereof. The secondary filler is selected from the group consisting ofclay, calcium carbonate, magnesium carbonate, silica powder and mixturesthereof. It is entirely unexpected that the particular combination ofdiallyl carbonate and reinforcing fillers would result in theimprovement in strength properties and stain resistance over prior artpolymers including diallyl carbonate polymers without the filler.

PREFERRED EMBODIMENTS OF THIS INVENTION The composition of thisinvention preferably comprises an intimate blend of at least 40 weightpercent of a reinforcing filler based on the weight of the compositionand still more preferably fillers in an amount of about 50 to 65 percentwith the balance being a polymer consisting of at least 50 weightpercent diallyl carbonate. While the diallyl carbonate polymericcomponents of this invention can contain other comonomers such asdiallyl phthalate, these other comonomers have been found to beunnecessary to achieve the desired improved results. Therefore, in thepreferred compositions of this invention diallyl carbonate homopolymeris used.

The primary fillers that have been found to be especially effective inthe compositions of this invention include alpha cellulose, milled glassfibers between 1/10 inch and A inch in length, polyester flock soldunder the registered trademark Dacron and mixtures of these primaryfillers. They are inti- ASTM Properties Test Method Value RockwellHardness, on M Scale D-785-62 I00 Flexural Strength, psi. D-790-63 7,500Flexural Modulus, .s.iv D-638-6 l T 850,000 Stain Resistance, ColorChange less than 40' expressed in R units on a Gardner Color DifferenceMeter A preferred composition of this invention especially suitable fordinnerware application consists of:

a. about 35 to 60 weight percent of diallyl carbonate homopolymer,

b. about 10 to 40 weight percent of one or more of the primary fillersof the type described in this section above, and

c. about 10 to 40 weight percent of finely divided clay, wherein thetotal of the (b) and (c) components are equal to at least 40 percentbased on the weight of the final composition. This particularcomposition not only has been found to have at least the minimumstrength properties listed in the preceding paragraph, but has beenfound to have a stain resistance of less than 15 expressed as a colorchange in R, units on the Gardner Color Difference Meter. Specificexamples of these compositions and results therefrom are set forth inthe Examples below.

One of the methods for preparing the diallyl carbonate monomer which isone of the alkyl esters and more specifically an ally] carbonate,comprises treating an excess of diethyl carbonate with allyl alcohol atreaction conditions to exchange the allyl radical of the alcohol for theethyl radical of the carbonate illustrated by the following equation:

This reaction preferably is conducted in the presence of a catalyst suchas the alcoholates of such alkali metals as sodium, potassium, lithiumand the like and the lower alcohols such as methyl, ethyl, butyl,isobutyl and propyl alcohol. For a typical reaction about 1 mole ofcatalyst is employed for 100 moles of diethyl carbonate. Althoughsolvents are not required to carry out the reaction, they may aid theprocess. Suitable solvents include benzene, hexene, dioxane, pentane andmixtures thereof. The preferred operating conditions includetemperatures in the range of about 60 to 160 C. for a period of about 3to 8 hours under a blanket of inert gas such as nitrogen. At thecompletion of the reaction the lower boiling alcohol is removed from thereactor by distillation. The diallyl carbonate monomer containing excessreactants, catalyst and the like can be purified by any suitable means.For additional details of this preparation reference can be made to US.Pat. No. 2,514,354.

Another method for preparing diallyl carbonate monomer comprisestreating an excess of allyl chloroformate with allyl alcohol in thepresence of an acid acceptor such as pyridine at reaction conditions tochemically exchange radicals as represented by the following equation:

A specific example of the synthesis of the diallyl carbonate monomer andits subsequent prepolymerization is set forth in Example 1 below.

The diallyl carbonate monomer is prepolymerized in the presence of asuitable solvent such as dioxane with a suitable initiator, i.e., aperoxide initiator such as di-tertiary butyl perbenzoate, di-tertiarybutyl peroxide, di-benzoyl peroxide, dilauroyl peroxide, cyclohexanoneperoxide, tertiary-butyl hydroperoxide, di-acetyl peroxide, dibenzoylperoxide, cumene hydroperoxide, dicumyl peroxide and the like, at atemperature of about 25 to 160 C. for a sufficient period of time topolymerize 10 to 50 weight percent, preferably 20 to 35 weight percentof the monomer to prepolymer. The resulting prepolymer product solutionis then cooled and precipitated with a nonsolvent and the resultingproduct is separated from the liquid phase and dried.

The resulting prepolymer is dissolved in a suitable solvent such asacetone to which is added the desired filler, one or more of theperoxide initiators and a metallic stearate as a processing aid such aszinc, magnesium, calcium and sodium stearate. In addition to thesecomponents, other components which can be added to incorporate them intothe compositions of this invention include pigments, delustrants,plasticizers, flame retardant materials and other materials known in theart to modify the chemical and physical properties of the finishedfilled diallyl carbonate compositions.

The mixture resulting from the combination of the above components isallowed to dry to remove the solvent. The resulting solid compositioncan then be ground or otherwise reduced into discrete particles and soldas a molding compound or molded into the desired articles.

The composition of the invention may be mixed in any suitable blendingapparatus, such as a cone-type mixer, double-arm mixer or the like toprovide intimate contact between the blending components.

The examples below illustrate the preparation of the com position of thepresent invention and the results obtained thereon.

EXAMPLES EXAMPLE 1 This example illustrates the synthesis of diallylcarbonate monomer and its subsequent prepolymerization for use in thecompositions of the examples below.

2.1 mols of allyl chloroformate were reacted in an agitated vessel with2 mols of allyl alcohol in the presence of pyridine at 3 to 10 C. for aperiod of about 5 hours. The resulting diallyl carbonate was recoveredfrom the vessel and washed, dried and distilled.

Sixteen grams of benzoyl peroxide were dissolved in 400 grams of1,4-dioxane and 400 grams of the diallyl carbonate were added to theresulting solution. The reaction mixture was heated from 25 to C. in 2hours and maintained at 80:t5 C. for about 2 hours to prepolymerizeabout 30 percent by weight of the monomer. The product mixture wascooled to 30 C. and mixed with methanol at 0 C. to precipitate thediallyl carbonate prepolymer. The solid prepolymer was separated fromthe liquid phase and dried.

EXAMPLE 2 About grams (about 66 percent based on the weight of the finalcomposition) of the diallyl carbonate (DAC) prepolymer of Example 1 weredissolved in grams of acetone. The following components were then addedto the solution: 3 grams of TiO pigment, 2 grams of zinc stearate toserve as a processing aid, 3 grams (about 1 percent based on the weightof the solution) of t-butyl perbenzoate, and 43 grams (about 29 percentbased on the weight of the final composition) of alpha cellulose flocksold under the trade name Solka Flock SW 40" and blended in a HobartMixer.

The resulting mixture was dried in a heated chamber for about 1 /2 hoursto remove the acetone. The dried material was then further blended in atwo-roll rubber mill for a period of about 5 minutes until it was wellmixed. The resulting material was then broken into small pieces andcompression molded under a pressure of 3,200 p.s.i.g. Compressionmoldedsamples, prepared by placing the material in the molds and heating thematerial at 300 F. for 2.5, 4, 6 and 8 minutes, respectively, were foundto have average Rockwell Hardness values on the M" Scale in the range of105-11 1. In addition, cups were molded from the composition of thisExample and measured for coffee stain resistance. The coffee stainresistance test comprised placing samples of the moldings in a bath ofcoffee containing 98 grams of fresh coffee grounds per 7,000 ml. H O at180 F. for a period of 48 hours. The degree of staining was measured bydetermining the color of the samples before and after exposure to thecoffee bath with a Gardner Color Difference Meter. The cups from thecomposition of the Example were found to be much more resistant tocoffee staining than cups molded from standard melamine-formaldehyderesin.

EXAMPLE 3 This example illustrates the effect of variations in thet-butyl perbenzoate concentrations during the thcrmosct polymerizationof the composition of this invention.

The same procedure followed in Example 2 was followed in this Examplewith the formulations set forth in Table l:

TABLE I Components Run 1 Run 2 Run 3 Run 4 DAG prepolymer, grams 50 72.2%) 40. 70. 6%) 38. 0 72. 2%) 38. 0 70. 2%) Acetone, grams 55 40. 0 38.0 38. 0 T102, grams 1. 2

Zinc stearate, grams 0. 8

t-Butyl perbenzonte, grams 0 I: Alpha cellulose, grams 16. 7 24. 2%) 13.4 23. 7%) 12.7 23. 8%)

Total 124. 2 96. 6

1 Prepared by the procedure of Example 1. 2 Based on weight of finalcomposition. 3 Based on weight of solution. H 7

Compression molded samples after mold times of 2, 4, 6, 8 COMPONENTS RUNand 10 minutes at 300 F. for Runs 1,2, 3 and 4 were found to haveaverage Rockwell Hardness values on the M Scale in DAC prepolymer" 40401% r the ranges indicated in the Table 11 below: 15 DAC 5 Acetone 75t-hutyl perhenzoate 1.35 TABLE II Tioz 215 Zinc stearate 0.5 Clay" 33.7131x01) Run Range of Rockwell Hardness Glass fiberu (M90; P

on M Scale 2 Notes: Based on the weight of the final composition 397-102 2 4 102-]04 5 "Prepared by the procedure of Example l "'Analuminum silicate pigment clay having an average particle size of about5 microns and sold under the trade name Clay ASP 400" Two-inch moldeddiscs from each of the molded samples of "'%inch milled glass fibers (EGlass) the compositions of Example 3 were cut in half and suspended in a1 percent aqueous solution of Alconox detergent. The The compressionmolded Samples of this example were 0 temperature of the Alconox bathwas m'fnmamed at 180 found to have an average Rockwell Hardness in therange of Random checks were made at 24-hour intervals to observe mo and104 on t.

breakage and water uptake. After 1 15 hours all of the samples wereremoved from the bath and were examined to show that specimens of thecompression moldings from the composi Sofiening had taken Place- A 1Percent aqueous Solu' tion of this example were immersed in coffeecontaining two tion was prepared and the test continued. After a totalof 12 teaspoons per cup at F for 48 hours and resulted in a days theSamples l" f their we'ght final color change of 8.7, expressed in R,,units which measured Q mmal welghts The Percent sures whiteness, fromthe specimens initial color as measured Crease "2 figh ofeachfof thiiseslampltesgvere l g j f a 40 by a Gardner Color Difference Meter ascompared to an R,, range 0 or sdmP as a t 6 m0 color change of about 43for standard melamine-formalabove are indicated in Table II] below:dehyde resins- TABLE I11 EXAMPLE 5 This example illustrates the resultsobtained on varying the HYDROLYTIC STABILITY type of filler used in thecompositions ofthe present invention. The formulations of Table IV belowwere prepared in accgrdancewith the procedure of Example 2:

TABLE IV Components Run 6 Run 7 Run 8 DAC prepolymer grams 35. Acetone,grams 7 0 Zinc stearate, grams. T102, grams 1. 8 t-Butyl perloenzoate,grams 1.05 Clay grams 25. 4 Calcium carbonate, grams 0 25.4 32. 9%) 2Alpha cellulose, grams 12. 7 16. 7%) 12.7 16. 5%) 12. Glassfiber 0 0 4'(hmfi) 7 14.16% 12.7 14.16%)

1 Prepared by procedure of Example 1.

2 Based on the weight of the final composition. 3 "Clay ASP 400.

4 milled glass (E glass).

243-163 The range of average Rockwell Hardness values for the 1 i 333:3;molded samples at mold times of 2, 4, 6 and 8 minutes, respec- 4 tively,are set forth in the Table below:

TABLE V EXAMPLE 4 This example illustrates more clearly the improvementin the stain resistance of the composition of the present inven- RUNRmge k f'g f'rfi tion when compared with standard grades ofmelamine-foron maldehyde resins.

v 6 90-99 The same procedure followed in Example 2 was followed 1n 7094" this example except that the following formulation in grams 8 -111was employed: I

TABLE VI RUN Color Difference. R

The results of this example further illustrate that excellent colorresistance and hardness can be obtained by the compositions of thisinvention.

EXAMPLE 6 This example shows a more complete breakdown of the strengthproperties of the compositions of this invention. The followingformulation in grams was prepared.

COMPONENTS RUN 9 DAC prepolymer l (42.0% Acetone 65 Zinc stearate 0.6

TiO l0.8

t-butyl perbenzoate L53 Alpha cellulose l9.l (5.76%)" Calcium (31.4%

Prepared by procedure of Example 1 "Based on the weight ofthe finalcomposition The procedure followed to obtain the composition of thisexample comprised dissolving the prepolymer in the acetone and thenadding to the mixture the t-butyl perbenzoate and thoroughly mixing thesolution. The solution was then introduced into an Atlantic Researchtwin-cone mixer and the zinc stearate, TiO and calcium carbonate wereadded. The mixture was then stirred for about 5 minutes and the alphacellulose was added followed by continuous mixing for an additional 10minutes. The acetone was partially evaporated by warming the mixtureslightly above room temperature and passing nitrogen over the mixture.The resulting composition was extruded into a Pyrex baking dish andallowed to dry overnight. The composition was then ground into a powder.A 5 inch X 8 inch l8 inch sheet was molded from the powder using aplatten temperature of about 305 F. and a pressure of about 100,000pounds for a mold time of 4 minutes. 1 inch X V2 inch wide strips werecut from the sheet and the following results were obtained:

Average flexural strength Average flexural modulus X [0" AverageRockwell hardness on the M Scale Average l'md impact strength Coffeestain resistance. R

9,320 p.s.i. l.() p.s.i.

l l l 0.24 ft.lbs./in. notch Expressed a a differential between theinitial and final color based on the same procedure discussed in Example5 above.

EXAMPLE 7 This example illustrates the use of polyester fiber as one ofthe fillers in the composition of this invention. The following Acetone75 Zinc stcarate l.(l

TiO, |5.0

t-butyl perhenniate l.ll5

Calcium carbonate 00.0 32.0".

Dacron polyester flock 30.0 (lo-15W) Total: 25711.

PRepared by procedure ofExample l Based on the weight ofthe finalcomposition The resulting mixture was placed on a baking dish to dry andthe compound was then ground into powder. Discs of 41 inch X 2 inchdiameter were molded from the powder at about 300 F. and at 3,100p.s.i.g. for a mold time of4 minutes. The physical properties of themoldings of Run 10 of this invention were compared with moldings ofcommercial melamine-type resins in Table Vll below:

TABLE VII Commercial Melamine- Type Resin RUN I0 Average RockwellHardness on the M" Scale H4 Average Izod Impact Strength. ft.lbs.lin.notch 0.25 0.53 Average Flexural Strength. p.s.i. H.800 8.200 AverageFlexural Modulus l0". p.s.i. l.32 0.86

The coffee stain resistance of the above two samples were determined bythe same procedure under Example 5 above. The composition of Run 10 wasfound to have greater stain resistance on visual inspection than thecommercial melaminetype resin. This was especially noticeable on the cutedges which shows the improved wick effect of the compositions of thisinvention over prior art compositions.

The foregoing examples have shown the unexpected improvement in thestain resistance of the compositions of the present invention whencompared with standard commercial grades of melamine-formaldehyderesins. In addition, the strength properties for the presentcompositions are on the same high level of melamine-type resins whichmake them ideally suited for dinnerware applications.

Resort can be had to modifications and equivalents within the spirit ofthe invention and the scope of the appended claims.

What is claimed is:

1. As an article of manufacture, dinnerware comprising an intimate blendof the following components:

a. about 35 to 60 weight percent of a homopolymer of diallyl carbonate,

b. about 10 to 40 weight percent of a primary filler selected from thegroup consisting of alpha cellulose, glass fibers, polyester fibers andmixtures thereof, and

about 10 to 40 weight percent of a secondary filler selected from thegroup consisting of finely divided clay, calcium carbonate, and mixturesthereof, the total of said components (b) and (c) being equal to atleast 40 weight percent based on the weight of the final composition,the final composition having the following minimum physical properties:A Rockwell Hardness on the M" Scale based on ASTM D-785-62 of I00, aflexural strength based on ASTM D-790-63 of 7,500 p.s.i., a flexuralmodulus based on ASTM D638-61T of 850,000 p.s.i. and a stain resistanceof less than 40 expressed in R,, units on a Gardner Color DifferenceMeter.

2. The article of claim 1 wherein said component (c) comprises finelydivided clay.

3. The article of claim 1 wherein said component (c) comprises finelydivided calcium carbonate.

4. As an article of manufacture, dinnerware comprising an intimate blendof the following components:

about 35 to 60 weight percent ofa homopolymer of diallyl carbonate,

b. about l to 40 weight percent of a primary filler selected from thegroup consisting of alpha cellulose, glass fibers, polyester fibers, andmixtures thereof, and

. about 10 to 40 weight percent of finely divided clay, the

the following components:

about 35 to 60 weight percent of a homopolymer of diallyl carbonate,

b. about 10 to 40 weight percent ofa primary filler selected from thegroup consisting of alpha cellulose, glass fibers, polyester fibers andmixtures thereof, and

about 10 to 40 weight percent of a secondary filler selected from thegroup consisting of finely divided clay, calcium carbonate and mixturesthereof, the total of said components (b) and (c) being equal to atleast 40 weight percent based on the weight of the final composition,the final composition having the following minimum physical properties:a Rockwell Hardness on the M Scale based On ASTM D-785-62 of 100, aflexural strength based on ASTM D-790- of 7,500 p.s.i., a flexuralmodulus based on ASTM D-638-61T of 850,000 p.s.i. and a stain resistanceof less than 40 expressed in R,, units on a Gardner Color DifferenceMeter.

6. The composition of claim 5 wherein said component (c) comprisesfinely divided clay in an amount of about 10-40 percent by weight ofsaid composition.

2. The article of claim 1 wherein said component (c) comprises finelydivided clay.
 3. The article of claim 1 wherein said component (c)comprises finely divided cAlcium carbonate.
 4. As an article ofmanufacture, dinnerware comprising an intimate blend of the followingcomponents: a. about 35 to 60 weight percent of a homopolymer of diallylcarbonate, b. about 10 to 40 weight percent of a primary filler selectedfrom the group consisting of alpha cellulose, glass fibers, polyesterfibers, and mixtures thereof, and c. about 10 to 40 weight percent offinely divided clay, the total of said components (b) and (c) beingequal to at least 40 percent based on the weight of the finalcomposition, the final composition having the following minimum physicalproperties: a Rockwell Hardness on the ''''M'''' Scale based on ASTMD-785-62 of 100, a flexural strength based on ASTM D-790-63 of 7,500p.s.i., a flexural modulus based on ASTM D-638-61T of 850,000 p.s.i. anda stain resistance of less than 15 expressed in Rd units on a GardnerColor Difference Meter.
 5. A composition of matter comprising anintimate blend of the following components: a. about 35 to 60 weightpercent of a homopolymer of diallyl carbonate, b. about 10 to 40 weightpercent of a primary filler selected from the group consisting of alphacellulose, glass fibers, polyester fibers and mixtures thereof, and c.about 10 to 40 weight percent of a secondary filler selected from thegroup consisting of finely divided clay, calcium carbonate and mixturesthereof, the total of said components (b) and (c) being equal to atleast 40 weight percent based on the weight of the final composition,the final composition having the following minimum physical properties:a Rockwell Hardness on the ''''M'''' Scale based On ASTM D-785-62 of100, a flexural strength based on ASTM D-790--of 7,500 p.s.i., aflexural modulus based on ASTM D-638-61T of 850,000 p.s.i. and a stainresistance of less than 40 expressed in Rd units on a Gardner ColorDifference Meter.
 6. The composition of claim 5 wherein said component(c) comprises finely divided clay in an amount of about 10-40 percent byweight of said composition.